Compound and method

ABSTRACT

Novel rhodium complexes having formula HRhCO(L(OR)3)3 are produced by reacting XRhCO(L(OR3)2, L(OR)3 and a metal borohydride under controlled conditions. In the formulae, L is As, Sb or P; R is alkyl and/or aryl; X is a halogen. The complexes are rate improving hydroformylation catalysts.

United States Patent Keblys Sept. 23, 1975 [54] COMPOUND AND METHOD3,644,446 2/1972 Booth et al. 260/429 R Inventor: Kestutis A. ysouthfield, 3,652,614 3/1972 Dewhlrst 260/429 R Mi h, OTHER PUBLICATIONS[73] Assignee. Ethyl corporafiml Richmond Pruett et al., J. Org. Chem.,34, (1969), p. 327-330. Pruett et al., Chem. Abstracts, 70 No. 86957.[221 FIIedI July 25, 1973 Chemical Abstracts 70 (1969), p. 28728. [2App] 3 2 377 Am. Chem. Soc. Abstracts of Meeting, 154 (1967), p.

N. (No. 39). Related US. Application Data [63] Continuation-impart ofSer. No. 32,347, April 27, P i a y Examiner Arthur P. Demers abandoned-Attorney, Agent, or FirmDonald L. Johnson; Robert A. Linn [52] US.Cl..... 260/429 R; 252/431 P; 260/604 HF [5 Int. Cl- 58 F' ld IS h 26029 R 1 le 0 Novel rhodium complexes having formula I-IRhCO[L- [56]References Cited (OR) are produced by reacting XRhCO[L(OR UNITED STATESPATENTS L(OR) and a metal borohydride under controlled conditions. Inthe formulae, L is As, Sb or P; R is alkyl 1:; fl f f l and/or aryl; Xis a halogen. The complexes are rate y 3X 1e 3.560.539 2/1971 Booth260/429 R lmpmvmg hydroformylauon catalysts 3,631,111 12/1971 Tucei260/429 R 17 Claims, No Drawings COMPOUND AND METHOD CROSS-REFERENCE TORELATED APPLICATION This application is a Continuation-in-Part ofcopending application Ser.'No. 32,347, filed Apr. 27, 1970 nowabandoned.

BACKGROUND OF THE INVENTION This invention is directed to novel rhodiumcomplexes, exemplified by HRh(CO)[P(OO) a method for their preparationand their use as hydroformylation (oxo) catalysts.

Rhodium complexes having the formula HRh(CO)(PR wherein R is an arylgroup, are known hydroformylation catalysts. Methods for preparing thesecomplexes are described in articles by S. S. Bath and A. Vaska, J. Amer.Chem. Soc., 85, 3500 1963); and D. Evans, G. Yagupsky and G. Wilkinson,J. Chem. Soc., A. 2660-2664 (1968); and their use as hydroformylationcatalysts is disclosed in articles by P.

S. Hallman, D. Evans, J. A. Osborn and G. Wilkinson, Chem. Commun.305-306 (1967); D. Evans, J. Osborn, and G. Wilkinson, J. Chem. Soc., A,3133-3142 (1968); C. K. Brown and G. Wilkinson, Tetrahedron Lett., 1725-1726 (1969); and R. L. Pruett and J. A. Smith, J. Org. Chem,, 34 327-330(1968).

In the Pruett and Smith article, a speculative mechanism for reactionsoccurring in a hydroformylation reaction wherein rhodium on carbon blackin the presence of excess hydrocarbyl phosphite or phosphine is used asthe catalyst, is described. The reaction equa- I the type represented byformula HRh(CO)[P(OR do exist; they are prepared using a novel process;and they are active hydroformylation catalysts.

SUMMARY OF THE INVENTION Complexes having the formula HRh(CO)[L(OR)wherein L is P, As, or Sb, and R is alkyl and/or aryl; a methodfor'preparing said complexes from XRh(CO)[ L(OR) '(whereiri X isahalogen), a stoichiometric amount, based on XRh(CO)[L(OR),,] of L(OR)and a metal borohydride in an alkanol solvent at temperatures of about-20C. to about 30C.; a hydroformylation process utilizing said-complexesas catalysts.

DESCRIPTION OF THE PREFERRED EMBODIMENT One embodiment of the presentinvention is compounds having theformula HRh( O)IL( 1)( z-X ana whereinL is selected from P, As, and Sb, and R R R are independently selectedfrom the groups consisting of alkyl, alkaryl, aryl and aralkyl, saidgroups having from 1 to about 18 carbon atoms. Compounds of formula Iwherein L is phosphorus are preferred; while more preferred compoundsare those of Formula I wherein L is phosphorus and R R R are aryl andalkaryl groups; and aryl and alkaryl groups may be substituted orunsubstituted and preferably include phenyl as the aryl moiety. Morepreferred compounds of Formula I are those in which L is phosphorus andR R R are the same. I

The novel compounds of the present invention are hydridorhodium carbonylcomplexes having Formula I wherein L is P, As, or Sb, and R R R arealkyl and- /or aryl groups. The alkyl groups include substituted andunsubstituted alkyl groups as well as linear and branched alkyl groups.Acyclic and alicyclic alkyl groups are also included. Illustrative ofsubstituents on substituted alkyl groups are phenyl, halogen, C -Calkoxy, cyano and nitro groups. Aryl groups likewise include substitutedas well asa unsubstituted groups. Illustrative of substituents onsubstituted phenyl groups are halogen, C -C alkoxy, cyano, nitro and C,Calkyl groups. The total number of carbon atoms in said alkyl and/or arylgroups is not critical; and alkyl and aryl groups having up to about20.carbon atoms are preferred.

The novel compounds are exemplified by complexes having Formula Iwherein the ligand group L(OR )(OR )(OR is as follows:

Methyldiphenyl phosphite Butylisopropylphenyl phosphite Triethylphosphite Trieicosyl phosphite Tri-2-ethyl-n-hexyl phosphite Tri-indenylphosphite Tri-B-naphthyl phosphite Dicyclooctyl-n-decyl phosphiten-Propyldi-ptolyl phosphite Tri-m-nitrophenyl phosphiteTri-m-fluorophenyl phosphite Tri-m-trifluoromethylphenyl phosphiteTridodecyl phosphite Tricyclohexyl phosphite Dibutyl-fi-naphthylphosphite Trimethyl arsenite Tri-p-chlorophenyl arsenite Dipentylphenylarsenite Tri-o-tolyl arsenite Octadecyl-di-indenyl arseniteTri-2-methylbutyl arsenite Tri-( 2-chloroethyl )arseniteTri-(4phenyl-n-butyl)arsenite Trixylyl arsenite Sb -o@ Tri-p-nitrophenylantimonite Triindenyl antimonite Tri-a-naphthyl antimonite Tribenzylantimonite Tri-p-hexylphenyl phosphite Tri-p-butoxyphenyl phosphiteTri-a-naphthyl phosphite Tri-p-hydroxyphenyl phosphite Preferredcomplexes are those wherein L(OR )(OR )(OR is a phosphite. Mostpreferred complexes are those wherein L(OR )(OR )(OR is a phosphite andR R R are the same. Examples of such preferred complexes are:

Hydridorhodiumcarbonyltris( tri-p-cyanophenylphosphite) Hydridorhodiumcarbonyltris(tricyclohexylphosphite) Hydridorhodiumcarbonyltris(triethylphosphite) Hydridorhodiumcarbonyltris( tribenzylphosphite)Hydridorhodiumcarbonyltris(tri-p-bromophenylphosphite) 4Hydridorhodiumcarbonyltris(tri-p-methoxyphenylphosphite)Hydridorhodiumcarbonyltris( triheptylphosphiteHydridorhodiumcarbonyltris( triphenylphosphiteHydridorhodiumcarbonyltris(tri-m-nitrophenylphosphite)Hydridorhodiumcarbonyltris(tribiphenylylphosphite)Hydridorhodiumcarbonyltris(tri-p-trichloromethylphenylphosphite) Anotherembodiment of this invention is a novel process for preparing thecompounds having Formula I. The process comprises reacting a compoundhaving the formula metal borohydride with a substantially stoichiometricamount, based on the compound having Formula II, of a compound havingthe formula ill and a metal borohydride in a C C alkanol reaction mediumat temperatures ranging from about 20C. to about 30C. L and R inFormulae II and III are as defined above; X in Formula II is a halogenselected from chlorine, bromine and iodine. It is important in the novelprocess that (l) greater than stoichiometric amounts of the compoundhaving Formula 111 be avoided and (2) that the reaction temperatures bebelow about 30C.

The method for preparing the aforesaid compounds can be illustrated bythe following reaction equation:

C2-C alkanol It is apparent from the above equation that the overallreaction results in the addition of one L(OR') ligand to the replacementof the halogen X with hydrogen in the Formula II reactant. There is nochange in oxidation state of the rhodium during the course of thereaction since rhodium is +1 in both the Formula II reactant and in theresulting novel complex (Formula I).

It is clear then that the complexes of the present invention, asdescribed above, can be prepared by chosing appropriate reactants havingFormula II and Forn'iula Ill.

It is important, however, in carrying out the present method that amolar ratio of Formula II reactantzFormula III reactant be substantially1:1. By substantially, I mean that the molar ratio of Formula IIreactantzFormula III reactant can range from about 120.8 to about 121.1;with a ratio of 1:1 being most preferred. In other words an excess ofFormula III reactant must be avoided. V

The reaction of the present method is carried out in an alkanol medium.The reactants having Formulae II and III and the borohydride may besoluble in the alkanol medium. However, solubility of the reactants inthe alkanol is not necessary. Useful alkanols have from 2 to about 10carbon atoms and are preferrably monohydroxy alkanols Amyl alcohol,l-decanol, 2-ethyl-nhexanol, tert-butanol, 3-methyl-n-butanol are someexamples of useful alkanols. Alkanols having up to 6 carbon atoms arepreferred. The lower molecular weight C -C alkanols are more preferred,for example, ethanol, isopropanol, and n-pr opanol.

The amount of alkanol reaction medium may be varied over a wide range.Optimum amounts of alkanol for a particular reaction may depend on otherfactors such as solubility of the reactants for example. Where thereactants are readily soluble in the alkanol, then it may be convenientto use sufficient alkanol to dissolve the reactants. However, it is notnecessary that the reactants be readily soluble inthe alkanol; thereaction will proceed as readily when the reactants are simply dispersedin a suitable amount of alkanol.

The metal borohydride reactant includes compounds of the type M (Bl-1where M is a metal such as Li, Na, K, Be, Mg, Al, Ti, Zr, and the likeand n is the valence of said metal M; and compounds such as M"[l-IB(OCl-I and the like. Preferred borohydrides are the alkali metalcontaining compounds such as NaBH Na[HB(OCI-I KBH LiBH K[l-IB(OC HLi[l-IB(OCH and the like. NaBH is most preferred.

At least a stoichiometric amount of metal borohydride is used in thepresent process, that is at least one mole of borohydride per mole ofFormula II compound. Generally an excess up to twice this stoichiometricamount of borohydride is used. It is preferred that when an excess isused it should not be over 1.25 times the stoichiometric amount. Inother words, it is preferred to use up to about 1.25 moles of theborohydride in the reaction per mole of Formula II compound.

The reaction temperature must be maintained below about 30C. Generally,a reaction temperature ranging from about -C. to about C. can be used. Apreferred reaction temperature range is about 0C. to about 15C.

Compounds having Formula II are known and can be prepared by anysuitable method. One method for preparing Formula II-type compounds isdisclosed in an article by L. Vallarino, Jour. Chem. Soc. p. 2474(1957).

The following examples illustrate the process of the present invention.All parts are by weight unless otherwise indicated. The abbreviationmmoles used herein means millimoles.

EXAMPLE 1 Preparation of l-Iydrido Rhodium Carbonyl TrisTriphenylphosphite A suspension of 1.980 grams (2.52 mmoles) of in 19milliliters of ethanol was prepared; charged to a suitable vessel andcooled to 0 with stirring; then 0.787 grams (2.54 mmoles) of triphenylphosphite in 6 milliliters of ethanol were added. Next, 0.10 grams (2.63mmoles) of sodium borohydride powder were added and the suspension wasstirred at 0 for 80 minutes.

1990, and 1960 cm (medium, poorly resolved). In

Nujol mull, the yellow powder showed bands at 2040 (sharp) and in 19451950 cm (broad, poorly resolved). Nuclear magnetic resonance analysisgave a weak signal at about 19.71. Elemental analysis of the yellowpowder showed C 6l.9/o; H 4.68/o; the calculated elemental analysis forhydridorhodiumcarbonyltris (triphenylphosphite). RhC I-I O P is C62.2/o; H 4.35/o. The light yellow powder obtained as a product wasthereby identified as hydridorhodiumcarbonyltris(triphenylphosphiteSimilar results are obtained when the reaction is carried out at 20C.,-10C., 5C., or 30C. When potassium borohydride, aluminum borohydride,lithium borohydride, Na[l-IB( OCl-I or mixtures of similar borohydridesare used in place of the sodium borohydride in Example 1, analogousresults are obtained. Methanol, n-decanol, 2-ethylhexanol, tertbutanolor isopropanol when used in place of ethanol in Example 1 effectequivalent results.

EXAMPLE 2 Preparation of I-Iydrido Rhodium CarbonylTris(Tri-p-chlorophenylphosphite) To a suspension of 4.20 grams (4.23mmoles) of chlororhodiumcarbonylbis(tri-p-chlorophenylphospb ite),cooled to 0C. were added 1.755 grams (4.25 mmoles) oftris(p-chlorophenyl)phosphite in 13 milliliters of ethanol. Then 0.1grams (2.63 mmoles) of sodium borohydride was added. Immediate gasevolution occurred and themixture turned yellow. Incremental amounts ofsodium borohydride were added to the reaction mixture as follows: 0.06grams after 2 hours,

0.05 grams after 4.5 hours, and 0.02 grams after 6 hours. Total reactiontime was 6.5 hours and a total of 0.23 grams (about 6 mmoles of sodiumborohydride) was added during this period.

At the end of this time the reaction mixture was filtered; and a lightcolored solid was obtained. The solid was washed with ethanol, dried anddissolved in about 10 milliliters of benzene. The benzene solution wasfiltered and evaporated to about 6 milliliters. About 15 milliliters ofethanol was added thereto. This solution was then evaporated and a whitesolid and yelloworange semisolid gum precipitated. The mixture wastriturated with ethanol until all of the gum solidified. The mixture wasthen filtered and a light colored solid was obtained. This solid waswashed with ethanol and dried in vacuum. A 46/o yield (2.70 grams) ofpale yellow powder, melting point 8992C. was obtained. A benzenesolution of the yellow powder on infrared analysis showed bands at 2075cm (sharp), poorly resolved band cluster at 1995, 1975 and 1960 cm andweak bands at 1885, 1760 and 1640 cm. In Nujol mull, only 2 sharp bandsat 2030 and 1935 cm were observed. Elemental analysis of the yellowpowder showed C= 49.2/o; H= 3.32/o; CI 23.5/o. The calashydridorhodiumcarbonyltris(tri-p-chlorophenyl- Reaction S stemphosphi'te").

Following the procedure substantially as illustrated by Examples 1 and 2above, the following reaction sys- 5 tems produce the products asindicated.

Example 2 y Product Tritolylarsenite 1 mole Potassiuin. borohydride Inmethanol at -l5C.

. Reaction System EXAMPLE 4 Product Lithium borohyd ride In isopropanol,at 25C.

Reaction 'S zstem Example 5 Product c1Rr1coAZls-(o-@.@ 1 mole mmcoAs-(O--@ 73 As-(tD-Q-G 0.8 moles NaZHMCCH )J 1 In Q-octanol, 20C.

Reactflgn System Example 6 Product In r:cc:n ol, at

gggction S stem Example Z Product NAB 4 1.01 moles In cyclohexanol, at5C Exgmgle 8 Ro act ion fem Product BrRhCOEM-O-C HQJ 1 mole111211001551-oc n 7 Sb(-OCgH5)s 0.9 moles Mia-004119)] a, In2etlwlbutanol, at 18C.

Q Examgle 2 Reaction System Product IRncOEM-cH Q 7 1 mole nancpEPo-cm-Q)J P(-0-CH2- 1 mole 1.11311 In tert-butanol, at 2C.

7 Exmgle 10 Reaction System Product cmhcogfi-o- 010 7 1 moleHRncOAR-o-CME MJ P(-O- -CE 11):, 0.95 moles roan In ethanol, at 25C.

Exam 1e 11 g action System Product cmncoAR-o-a -CF3);72 1 moleHRhCOR-O-g-CFQJ NaBH In ethanol, at 15C.

- Reaction Sxstem Product BrRhcofiM-o--cH -cn -c1),,7 1 molemcoAKd-o-crg-cumkfl (acn -C an 1 mole LiBH In mixed amyl alcohols, at2C.

Examgle 12 Reaction Szstem Product d CH CH mam In Qwthybg-hexanol, at30C.

v Example 1 Reaction Svstem Product la as P(-o-@ 0.98 moles mam Inmethanol, at 29C.

EXAMPLE 15 Reaction System Product C R l2 25)u]2 1 mole HRhCO[As(OC, HAs(-OC, H, 1.02 moles man In hexanol-3, at 8C.

Examgle 16 Reaction System Product Br Br C1RhCO[1 (-O@-Br) 7 1 mole11121100111 -o@--Br);17=

rho-(D nk 1 mole L1BH In propanol, at -3C.

Examgle 11 Reaction System Product BrRhCQZfl-Q- J 1 mole rmncolfi-omFPO-ED 1.08 moles lie-EH In ethanol, at 29C.

In sec-butanol, at 0C.

13 Example, 12

Reaction Sym OH c1Rnco[F( -06 i 7 1 mole In heptanol, at -70C.

Example Reaction System Another embodiment of this invention is ahydroformylation process which comprises reacting a C C olefiniccompound having at least one alpha carbon-tocarbon double bond withcarbon monoxide and hydrogen under 1 to 500 atmospheres pressure in thepresence of a catalytic amount of the rhodium complex having Formula Iwherein (a) X is arsenic antimony or phosphorous and (b) R R R areindependently selected from alkyl and aryl groups having up to about 18carbon atoms. The product obtained from the hydroformylation reaction isaldehyde having at least one carbon atom more than the olefinicreactant.

A preferred hydroformylation process is the process described abovewherein the rhodium complex used as a catalyst has the formula where R RR are as defined above; a more preferred hydroformylation catalyst isthe Formula lV complex wherein R R R are the same. A most preferredcatalyst is a complex having the formula HRh(CO)[- P(OR) wherein R isphenyl or substituted phenyl group as disclosed herein.

Olefinic organic compounds which contain at least one non-aromaticcarbon-to-carbon double bond may be hydroformylated in the presentprocess. Preferred olefinic organic compounds are the olefins. Byolefins, I mean compounds having at least one alpha double bond. Usefulolefins include acyclic and cyclic olefins, branched and linear olefins,monounsaturated and polyunsaturated olefins, substituted andunsubstituted olefins. Examples of olefins which are suitable for use inthe present hydroformylation process are 4,5- dibromododecene,1,4,7-decatriene, 1,4-octadiene, 1,5-nonadecadiene, l-tridecen- 1 2-0],l,5,8-dodecatriene, 1,6-pentacosadiene, 2-isobutylhexene-l, 4,6,8trimethylnonene-l 4-chlorotetradecene-l 8- Product Productphenyloctene-l, and the like. Mixtures of olefins may also be used.

Particularly preferred olefins are C C olefins having one or more alphadouble bonds. The particularly preferred olefms having more than onealpha double bond are further characterized in that the double bonds areisolated, that is, separated by at least one carbon atom. Thus,preferred olefins are exemplified by compounds such as l,5-hexadiene,l-decene, 1,4-pentadiene, l-octadecene, l-heptadecene, l-tetradecene, 2-methylhexadecene, 1 ,22-tricosadiene, l l 3-tetradecadiene, cyclohexene,cyclooctene, 1,6- cyclododecadiene, l-butene and the like.

The olefins which are especially preferred are alpha monoolefins having2 through 32 carbon atoms. Examples of the especially preferredmonoolefins are ethylene, l-propene, l-pentene, 3-methylundecene,l-heptadecene, l-nonadecene, l-dotriacontene, l-eicosene,3,5-dirnethyldecene, and the like. Mixtures of monoolefins can also beused.

The catalyst which is used in the hydroformylation process of thisinvention is a rhodium complex having Formula I. This complex offers anadvantage in that it is sufficiently soluble in typical hydroformylationreaction solvents and/or in the olefinic reactants, and thus thereaction can be carried out in a homogeneous rather than a heterogeneoussystem.

The rhodium complexes which are suitable as catalysts are described andexemplified above in the disclosure relating to the complexes and theirmethod of preparation.

The hydroformylation reaction of this invention can be carried out in aliquid reaction medium. This liquid reaction medium is such that itshould not interfere with the desired hydroformylation reaction norreact with the products obtained therefrom. This liquid reaction mediumfurthermore is preferably a solvent for the catalyst and the unsaturatedorganic reactant. Examples of suitable media of this type arehydrocarbons such as benzene, toluene, Decalin, decane and the like,

and oxygenated organic compounds such as dimethyl carbitol, diisobutylketone and the like. Other organic media which meet the criteria setforth above can also be used. Where the olefinic reactant is liquidunder the reaction conditions, and the catalyst is sufficiently solubletherein, no other reaction medium is required. i

The hydroformylation process of this invention can be carried out attemperatures from about C. to about 120C. A preferred temperature rangefor the present reaction is from about 0C. to about 50C.; a mostpreferred range is about 20C. to about 50C.

This reaction can be carried out under pressures ranging from about 1 toabout 500 atmospheres. It is preferred that pressures from 1 to aboutatmospheres be used. Since the reactants, carbon monoxide and hydrogen,are gases under the conditions of this reaction, these gases can beordinarily used to maintain the desired reaction pressure. If necessary,however, the pressure may be maintained by using other inert gases, suchas nitrogen and the like.

Generally the time required to complete the reaction may be varied overa wide range. Reaction times from about 5 minutes to about 12 hours canbe used. The time of reaction is, however, to a certain extent, adependent variable. For example, as the temperature of the reaction isincreased, the reaction time may be decreased. Furthermore, batchprocesses would normally allow for longer reaction times, whereas acontinuous process would utilize a shorter time.

A molar ratio of COzl-l which should be maintained during the reactionis from about 1.511 to about 1:5. It is preferred that the CO: H ratiobe in the range of from about 1:1 to about 1:3. Reaction ratios of theCO and H outside the ranges given can also be used.

. The amount of catalyst which is used in the present hydroformylationprocess may be varied. Sufficient rhodium complex catalyst is used inorder that the reaction mixture is 0.005 to 0.1 molar with respect torhodium. A preferred molar concentration range for rhodium is 0.005 to0.02.

- The present process can also be carried out in the presence of anadded excess amount of L(OR) ligand.

The amount of L(OR) used may vary from 0.5 to 100 1 moles of L(OR) permole of ,HRhCO[L( OR)3]3 catalyst; the preferred L(OR) :HRhCO[L(OR)molar ratio is 20:1 to 1:2; while 5:1 to 1:2 is a more preferred molarratio,'and 3:1 is a most preferred molar ratio.

The rhodium complex used as a catalyst in the present hydroformylationprocess effects (1) lowtemperature and low pressure reaction and (2)greater selectivity with regard to increasing, the amount of linearaldehyde in the product. Ordinarily, hydroformylation of an C or higheralpha olefin produces-a mixture of aldehydes (having one carbon atommore than said olefin) which is about 60/o linear and about 40/obranched. For example, ordinary hydroformylation of butene-l using Co(CO) catalyst will yield a mixture of pentanals about 60/o of which aren-pentanal. In the present process the linear aldehyde content of thetotal aldehyde product is over 85lo.

Another outstanding feature of the present catalyst system is that iteffects a hydroformylation rate sub stantially greater than the twocomponent rhodium on carbon black/excess trihydridocarbylphosphitecatalyst 16 system disclosed in the aforesaid article by Pructt andSmith.

The following examples will illustrate the prsent hydroformylationprocess and the improvement in reaction rate over the Pruett and Smithcatalyst system. As used herein the term conversion refers to the amountof starting olefin which has reacted to produce aldehyde product; and itis expressed asper cent conversion (by weight). Per cent linearityindicates the proportion of linear aldehyde in the total aldehydeproduct.

EXAMPLE 2 Hydroformylation Using rmncofil -o@ 7 Catalyst A suitablereaction vessel was charged with 0.3187 grams(0.300 mmoles) of next 1 /2hours at 25C.; the H :CO ratio during this period was 3:1.

I Samples were withdrawn from the reaction mixture during the course ofthe reaction and analyzed by vpc (vapor phase chromatography) for olefinand aldehyde. The product obtained contained n-nonanal and2-methyloctanal-l. The results of the analysis of the samples which werewithdrawn are presented below:

Reaction Conversion, Time to C Linearity, Sample (hrs.) Aldehydes lo 1V2 12.4 /o 88.1 '2 1 25.6 /o 87.7 3 1% 33.6 f/o. 88.3 4 2 47.9 /o 88.6 52% 57.5 /o. 88.3 6 2% I 64.2 /o 88.4 7 p 3 77.4 /o 89.5 8 3% 85.6 [089.8 9 3% 86.5 /o 90.0 10 4 86.5 lo 89.5

EXAMPLE 22 Hydroformylation Using 5/o Rh on Carbon/ExcessTriphenylphosphite Catalyst A suitable flask was first flushed withnitrogen and then it was charged with 3.0 grams of 5/o rhodium on carbonblack (1.45 mmoles of rhodium), 3.0 gram"- (9.68 mmoles) oftriphenylphosphite, 22.4 grams (200 mmoles) of octene, 1.52 grams (7.16mmoles) of npentadecane (internal standard), and 40 millilitersoftoluene. Then H zCO was bubbled into the stirred mixture. in a 1:1 ratiofor 12 hours at room temperature (about 25C.); and the'linearity was90lo. The reaction was discontinued at the end of this time. Analysis ofthe reaction mixture by vpc showed. that 13.1 mmoles of n-nonanal and1.42 r'nmoles of 2-methy1octanal were present; which calculated to be73%) conversion. 1

EXAMPLE 23 'Bydrofomylation Using !mhCO/IP(-)g7s and Slight Excess ofTi'iphenylphosphfle A suitable reaction vessel wascharged with 0.3187grams (0.300 mmoles) of 0.0996 grams (0.322 mmoles) oftriphenylphosphite, 0.364 grams of nonane (an internal standard), 1.533grams of pentadecane (another internal standard) and 25 milliliters ofbenzene. Carbon monoxide was passed through the stirred mixture for 5minutesQThen the vessel was charged with 3.54 grams (31.5 mmoles) 30 ofoctene-l. The solution was stirred at 25 1': 0.5C. andmilliliters/minute each of hydrogen and CO was passed into the mixturefor 6.75 hours. Samples were withdrawn during the course of the reactionand analyzed by vpc. The results of the analysis are given below. Thealdehyde product was a mixture of C aldehydes containing n-nonanal and2-methyloctanall.

+ 'PiO-Qh' jabs-Q 4320 7}, and a 5 Y iSimilar results are obtained whenHRh(CO)-[As- (OC6H5)8]3 and 6 5)a; Haiti JO or HRh(CQ)[Sb(-O'C H I andSb(O-C H are used as the catalyst system in Example 23.

EXAMPLE 24 Hydrofonnylation Using HRhCO (O-) 7 and Larger Exeess'of'triphenylphosphite The Example 23 experiment was substantially repeatedexcept that the. amount oftriphenylphosphite was increased to 0.2637grams (0.850 mmoles); and the reaction was continued for 7 hours. Theresult of the vpc analysis of the samples withdrawn during the course'of this reaction are given below. The product was a mixture of Caldehydes containing n-nonanal and Z-methyloctanal-l ReactionConversion, Time, to C Linearity, Sample (hrs) Aldehyde lo l A 1.4 /o87.4 2 l 5.4 /0 86.9 3 2 1 1.3 /o 89.0 4 3 16.0 lo 87.9 5 4 20.0 /0 87.96 5 24.4 lo 88.3 7 6 28.7 l0 88.3 8 7 32.4 lo 88.3

Analogousresults are obtained in Example 24 when the reactiontemperature is 0C., 10C., 16C., or 50C.

The results obtained in Examples 21, 23-24 show the effectiveness of thepresent rhodium complexes as hydroformylation catalysts. A comparison ofthese results with the results obtained in Example 22 illustrates howmuch more effective the hydroformylation catalyst of the present complexis as compared with rhodium on carbon/excess hydrocarbylphosphite. Forease of comparison, the results from Examples 21-24 are presented in thefollowing table:

. Molar Ratio Reaction Rh: P( O-@ Time Conversion 1:6" 12 hrs. 7.6/o

15 3-2/3 hrs. 86.5/o

1:6 (1) 7 hrs. 32. 1%)

1: .6-3/ l hrs. 58.5/c

included P(O-) contained in complex.

It is clear from the data in Table A that the rhodium complex catalysteffects an unexpectedly greater rate of reaction than the rhodium oncarbon black system. The olefin conversion using the present complex(Example 21 is 86.5/o after only 3% hours; olefin conversion using therhodium on carbon/triphenylphosphite catalyst (Example 22) is only7.6/o, after 12 hours.

Furthermore, even when the rhodiumzphosphite molar ratio, using thepresent complex, is raised (by the addition of phosphite to the reactionmixture) to the 1:6 molar ratio level of Example 22, olefin conversionis still significantly higher viz. 32.4/o Example 24 vs. 7.6/o Example22.

EXAMPLE 25 Reaction Conversion, to Linearity, Sample Time (hrs) CAldehyde /o 1 A 15.1 /o 83.0 2 1$ 30.2 /o 83.8 3 $41 45.0 /o 83.8 4 148.5 lo 83.4 5 1% 49.7 /o 81.5 6 1% 50.6 l0 80.9

Besides conversion of olefin reactant to aldehydes, the catalyst systemof the present invention also isomerizes the olefin, to a certainextent. The isomerization involves shifting of the double bond withinthe olefin molecule. Thus, e.g. besides C aldehydes, octene iso-' merssuch as octene-2, octene-3 and the like are also found in the productsin Examples 21, 23-25. This isomerization generally increases withincreasing temperature.

Similar results are obtained when equivalent amounts of other rhodiumcomplex compounds (as described and extensively exemplified hereinabove)are used as catalysts in the hydroformylation processes illustrated byExamples 21, 22-25. This includes the As and Sb analogs of the Pcontaining complexes. As pointed out above, the complexes containingphosphite ligand (as described and exemplified above) are more preferredas catalysts in the present process.

The molar concentration of rhodium in Examples 21 23-25 is 0.01 or 0.03.Analogous results are obtained when the amount of rhodium complex usedin these Examples provides a rhodium molar concentration of 0.1, 0.008,0.05, 0.09, or 0.025.

The reactions in these Examples may also be carried out at pressuresabove atmospheric, for example, 10 atmospheres, 100 atmospheres, or 50atmospheres; but the reaction rate, as compared to the rate atatmospheric pressure, is somewhat reduced.

The reactions of Examples 21, 23-25 proceed in an analogous manner whenthe reaction temperature is 1C., 18C., 100C., 80C., or 60C.

Substituting the following olefin reactants in the processes exemplifiedabove gives aldehyde products, as

indicated. The linear aldehyde content of the aldehyde products is overabout 85/o, in each case.

Olefin Reactant Aldehyde Products Ethylene Propanal Tetracosene- 1Pentacosanal Z-Methyltetracosanill Dotriacontene-l Tritriacontanal-l2-Methyldotriacontanal Cyclohexene Cyclohexanal Styrene 3-PhenylpropanalZ-Phenylpropanal 2-Ethylhexene- 1 3-Ethylheptanal Tridecanall DodecenelZ-Methyldodecanal II I! 1,4-Pentad1ene H-c-( 3 l, fi-Dimetnylpentanedial2-Methy1hexanedial 2-Methy1-8-decenal The following two examplesfurtherillustrate the hydroformylation of the present invention carried outunder pressure.

EXAMPLE 26 Hydroformylation Under Pressure Using HRhCO[P(-O-C,,,l-lCatalyst The catalyst (0319' grams of was placed in a small test tubewhich was positioned on ing autoclave which was sealed and flushed wellwithcarbon monoxide. The autoclave was then pressured to 10 p.s.i. withcarbon monoxide and up to 85 p.s.i. with hydrogen (about 3:1 H :COratio). Then the autoclave rocking was begun and the reaction wasallowed to proceed in this way for two hours at 25C. (periodicallyduring this period the autoclave was repressured from 83 to 85 psi. witheither carbon monoxide or hydrogen as required to maintain 3:1 H :COratio). At the end of this time, the autoclave was vented and flushedwith carbon monoxide.

The product obtained was analyzed by vpc. Conversion to C aldehydes was45.5/o; and the linear C aldehyde content was /o.

EXAMPLE 27 Hydroformylation Under Pressure Using HRhCO[ p-ClC H P 3Catalyst Using substantially the same equipment and charging procedureas in Example 26, the following reagents were charged to a glass rockingautoclave liner: 0.2081 grams (0.151 mmoles) of HRhCO[(p-CIC HQ Ph, 3.55grams (3.16 mmoles) of 1-octene, 0.374 grams of nonane, 1.518 grams ofpentadecane, and 22.5 milliliters of benzene. The liner was then placedin an autoclave and it was flushed with carbon monoxide, sealed and thenpressured to 85 p.s.i. with hydrogen. (The H :CO ratio was about 3:1).The autoclave was then rocked and the reaction was continued under theseconditions for three hours at 23C. During this reaction period theautoclave was repressured twice with carbon monoxide from 83 to 85p.s.i. At the end of this time, the autoclave was vented and flushedwith carbon monoxide.

The product obtained was analyzed by vpc. Conversion to C aldehyde was/o; and linear aldehyde content was 92.3/o.

The aldehyde products from the hydroformylation are useful as chemicalintermediates. For example, the aldehydes can be oxidized to produce thecorresponding carboxylic acids; and these acids can be used to prepareesters which are useful as lubricants, plasticizers, and the like. Thealdehyde products are ordinarily mixtures of aldehyde isomers as pointedout above. These mixtures can be conveniently used as such; or ifdesired, they may be separated by any suitable means.

The present invention comprises three embodiments, namely, novel rhodiumcomplexes, a method for preparing such complexes, and a hydroformylationpro- .cess utilizing said novel complexes as catalysts. Theseembodiments have been fully described above. Claims to the inventionfollow.

I claim:

1. A method for preparing compounds having the formula l-lRh(CO)[L(OR)(OR )(OR wherein L is selected from P, As, and Sb, and R R and R areindependently selected from the groups consisting of alkyl and aryl,said groups having from one to about 20 carbon atoms, which comprisesreacting a. a compound having the formula XRhCO[L(OR, )(OR )(OR whereinX is a halogen and L, R R and R are as defined above,

b. a substantially stoichiometric amount based on compound (a) of acompound having the formula L(OR )(OR )(OR wherein L, R,, R and R are asdefined above, and

c. a metal borohydride in a C -C alkanol reaction medium at temperaturesranging from about 20C. to above 30C.

2. The method of claim 1 wherein L is phosphorous.

3. The method of claim 1 wherein R R and R are the same.

4. The method of claim 3 wherein L is phosphorous.

5. The method of claim 4 wherein R R and R are selected from hydrocarbonalkyl groups and substituted alkyl groups wherein said substituents areselected from phenyl,, halogen, C,C., alkoxy, cyano and nitro groups.

6. The method of claim 4 wherein R R and R are selected from phenyl andsubstituted phenyl groups wherein said substituents are selected fromhalogen, C -C alkoxy, cyano, nitro, phenyl and C,--C alkyl groups.

7. The method of claim 4 wherein R R and R are phenyl.

8. The method of claim 4 wherein R R and R are p-chlorophenyl.

9. The method of claim 2 wherein the molar ratio of XRhCO[(L(OR )(OR)(OR :metal borohydride is between l:l.l and about 1:2.

10. The method of claim 9 wherein said metal borohydride is selectedfrom alkali metal borohydrides and aluminum borohydrides.

11. The method of claim 10 wherein said metal borohydride is an alkalimetal borohydride.

12. The method of claim 10 wherein said alkali metal borohydride issodium borohydride.

13. The method of claim 2 wherein said alkanol is ethanol.

14. The method of claim 2 wherein said reaction temperature is betweenabout 0C. and 15C.

15. The method of claim 14 wherein said alkanol is ethanol and saidmethal borohydride is sodium borohydride.

16. The method of claim 15 wherein R R and R are phenyl.

17. The method of claim 15 wherein R R and R are p-chlorophenyl.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENT NO. 5,907,847

DATED September 23, 1975 |NV ENTOR(S) Kestutzis A. Keblys It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 12 that part, of the formula reading: F(OO) 7 should be(OQf) 7 Column 2, line 25 asa should be as Signed and Sealed thissixteenth D ay Of December 1 9 75 [SEAL] A ttest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj'Parentsand Trademarks

1. A METHOD FOR PREPARING COMPOUNDS HAVING THE FORMULAHRH(CO)L(OR1)(OR2)(OR3))3 WHEREIN L IS SELECTED FROM P, AS, AND SB, ANDR1, R2 AND R3 ARE INDEPENDENTLY SELECTED FROM THE GROUPS CONSISTING OFALKYL AND ARYL, SAID GROUPS HAVING FROM ONE TO ABOUT 20 CARBON ATOMS,WHICH COMPRISES REACTING A. A COMPOUND HAVING THE FORMULA XRHCOL(L(OR1)OR2)(OR2)(OR3) WHEREIN L, R1, R2, AND R3 ARE AS DEFINED AS DEFINEDABOVE. B. A SUBSTANTIALLY STOICHIOMERIC AMOUNT BASED ON COMPOUND (A) OFA COMPOUND HAVING THE FORMULA L (OR))( OR2)OR3) WHEREIN L, R1, R2, ANDAND R3 ARE AS DEFINED ABOVE, AND C. A METAL BOROHYDRIDE IN A C1-C6ALKANOL REACTION MEDIUM AT TEMPERATURES RANGING FROM ABOUT -20*C. TOABOVE 30*C.
 2. The method of claim 1 wherein L is phosphorous.
 3. Themethod of claim 1 wherein R1, R2, and R3 are the same.
 4. The method ofclaim 3 wherein L is phosphorous.
 5. The method of claim 4 wherein R1,R2, and R3 are selected from hydrocarbon alkyl groups and substitutedalkyl groups wherein said substituents are selected from phenyl,,halogen, C1-C4 alkoxy, cyano and nitro groups.
 6. The method of claim 4wherein R1, R2, and R3 are selected from phenyl and substituted phenylgroups wherein said substituents are selected from halogen, C1-C4alkoxy, cyano, nitro, phenyl and C1-C6 alkyl groups.
 7. The method ofclaim 4 wherein R1, R2, and R3 are phenyl.
 8. The method of claim 4wherein R1, R2, and R3 are p-chlorophenyl.
 9. The method of claim 2wherein the molar ratio of XRhCO((L(OR1)(OR2)(OR3))3:metal borohydrideis between 1:1.1 and about 1:2.
 10. The method of claim 9 wherein saidmetal borohydride is selected from alkali metal borohydrides andaluminum borohydrides.
 11. The method of claim 10 wherein said metalborohydride is an alkali metal borohydride.
 12. The method of claim 10wherein said alkali metal borohydride is sodium borohydride.
 13. Themethod of claim 2 wherein said alkanol is ethanol.
 14. The method ofclaim 2 wherein said reaction temperature is between about 0*C. and15*C.
 15. The method of claim 14 wherein said alkanol is ethanol andsaid methal borohydride is sodium borohydride.
 16. The method of claim15 wherein R1, R2, and R3 are phenyl.
 17. The method of claim 15 whereinR1, R2, and R3 are p-chlorophenyl.